Compositions for use in internal-combustion engines and methods of forming and using such compositions

ABSTRACT

A fuel composition for use in internal-combustion engines has a fuel component, an alcohol component, a water component, a microemulsion blend, and a cetane-enhancer component. The microemulsion blend includes at least one of lower grade fatty acid derivatives being present in an amount effective for the fuel, alcohol, and water components to form a microemulsion blend. The emulsifier is present in an amount effective for the biodiesel fuel, alcohol, water, and emulsifier to form an emulsion.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims the benefit under 35 U.S.C. §119(e) of U.S.Provisional Patent Application Ser. No. 62/332,435, filed May 5, 2016and is also a continuation-in-part of U.S. patent application Ser. No.15/153,623, filed May 12, 2016, each of which is hereby incorporated byreference in its entirely for all purposes.

U.S. patent application Ser. No. 15/153,623 is a continuation of U.S.patent application Ser. No. 14/216,810, filed Mar. 17, 2014 and entitledCOMPOSITIONS FOR USE IN INTERNAL-COMBUSTION ENGINES AND METHODS OFFORMING AND USING SUCH COMPOSITIONS, which application claims thebenefit under 35 U.S.C. §119(e) of U.S. Provisional Patent ApplicationsSer. Nos. 61/798,461 and 61/798,438, each filed Mar. 15, 2013, and eachof which is hereby incorporated by reference in its entirety for allpurposes.

U.S. patent application Ser. No. 14/216,810 is a continuation of U.S.patent application Ser. No. 13/966,207, filed Aug. 13, 2013 and entitledMETHOD OF FORMULATING A FUEL COMPOSITION FOR USE IN INTERNAL-COMBUSTIONENGINES, which application is a continuation-in-part of U.S. patentapplication Ser. No. 13/217,171, filed Aug. 24, 2011 and entitled METHODOF FORMULATING A FUEL COMPOSITION FOR USE IN INTERNAL-COMBUSTIONENGINES, which application is a continuation of U.S. patent applicationSer. No. 12/105,164, filed Apr. 17, 2008 and entitled METHOD OFFORMULATING A FUEL COMPOSITION FOR USE IN INTERNAL-COMBUSTION ENGINES,which application claims priority to U.S. Provisional Patent ApplicationSer. No. 60/974,779, filed Sep. 24, 2007 and entitled MICROEMULSION FUELCOMPOSITIONS AND METHODS FOR PRODUCING THE SAME and also claims priorityto U.S. Provisional Patent Application Ser. No. 61/036,007, filed Mar.12, 2008 and entitled FUEL COMPOSITIONS FOR USE IN INTERNAL-COMBUSTIONENGINES AND METHODS OF FORMING USING SUCH COMPOSITIONS, each of which isincorporated herein by reference in its entirety for all purposes.

TECHNICAL FIELD

The disclosure relates to the field of fuel compositions. Moreparticularly, the disclosure relates to fuel compositions and fueladditives for internal combustion engines.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic block diagram showing a new method forsynthesizing and formulating a fuel composition for use ininternal-combustion engines in accordance with the present invention.

FIGS. 2A-2C show a method and apparatus for formulating a fuelcomposition on large scale in accordance with the present invention.

FIGS. 3A-3B illustrate a blending apparatus for blending fuel andmicroemulsion blend for formulating fuel composition in accordance withthe present invention.

FIG. 4 show a storage container for storing a fuel composition made inaccordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides fuel compositions for use in internal-combustionengines, and methods of forming and using such compositions.

The fuel compositions generally comprise (1) a hydrocarbon fuel, such asdiesel, (2) a polar fluid, such as alcohol, water, and/or other oxygenrich fluids, (3) an emulsifier present in an amount effective for thehydrocarbon fuel, polar fluid, and emulsifier to form an emulsion; and(4) a cetane enhancer, such as 2-ethylhexyl nitrate. The emulsifier maybe selected from a group consisting of noncyclic polyol fatty acidesters and noncyclic polyol fatty alcohol ethers. In some embodiments,at least about half of the emulsifier is selected from this group. Inother embodiments, at least about half of this group ismono-substituted. The emulsifier also may consist essentially of asingle molecular species having both polar and nonpolar portions.

The methods generally comprise methods of forming and using the fuelcompositions, including components thereof. For example, the inventionprovides methods of forming the emulsifier, by synthesizing and/orpurifying components of the emulsifier. These components may includenoncyclic polyol fatty acid esters and noncyclic polyol fatty alcoholethers.

These and other aspects of the invention are described in the followingfour sections: (1) synthesis of noncyclic polyol fatty acid esters andnoncyclic polyol fatty alcohol ethers, (2) purification of noncyclicpolyol fatty acid esters and noncyclic polyol fatty alcohol ethers, (3)fuel compositions, and (4) examples.

Monoglycerides of fatty acids have been used for years as surfactants ina variety of food, cosmetic, and other formulated products. In mostapplications, industrial-grade monoglyceride compositions having 40-55%monoglyceride content have proven suitable. However, the presentapplication in fuel formulations requires high-purity monoglycerides toyield optimal performance, and inexpensive monoglycerides to beeconomically practical.

Monoglycerides have been synthesized by a variety of methods.Unfortunately, these methods generally yield products that must befurther distilled or extracted to obtain high-purity monoglycerides.Moreover, these methods generally are unsuitable for formingmonoglycerides of unsaturated fatty acids, such as oleic acid, becauseof oxidative decomposition at the point of unsaturation. U.S. Pat. No.2,022,493 to Christensen et al. discloses the conventional method forsynthesizing monoglycerides, which involves the transesterification oftriglycerides with glycerol and sodium hydroxide to form themonoglycerides. However, the product of this method is a mixture of40-55% monoglyceride, 20-30% diglyceride, and a remainder of unreactedtriglyceride. U.S. Pat. No. 2,132,437 to Richardson et al. and U.S. Pat.No. 2,073,797 to Hilditch et al. disclose two methods of increasingmonoglyceride selectivity by converting the triglyceride to free fattyacid before esterification. However, the products of these methods arestill contaminated with at least 20% di- and triglyceride, and themethods are considerably more complex than the conventional method. U.S.Pat. No. 5,153,126 to Schroder et al. discloses a method for makingadditional gains in selectivity by using a lipase enzyme as thetransesterification catalyst. However, this method is very costly anddifficult to scale up.

A fuel composition for use in internal-combustion engines has a fuelcomponent, an alcohol component, a water component, a microemulsionblend, and a cetane-enhancer component. The microemulsion blend includesat least one of lower grade fatty acid derivatives being present in anamount effective for the fuel, alcohol, and water components to form amicroemulsion blend. The emulsifier is present in an amount effectivefor the biodiesel fuel, alcohol, water, and emulsifier to form anemulsion.

FIG. 1 shows a new method 100 for synthesizing and formulating a fuelcomposition for use in internal-combustion engines. At step 102 a fuelis provided, the fuel is non-renewable content in the fuel composition.The fuel can be diesel. A non-renewable content is selected. Thenon-renewable content may include lower grade fatty acid derivatives (orsurfactant) and/or other surfactants. At step 104, an alcohol componentsuch as, but not limited to, lower grade ethanol (i.e. hydrous ethanol,and so forth) may be provided. Then at step 106, a microemulsion blendhaving at least one of lower grade fatty acid derivatives is provided.The steps 102 to steps 106 can be performed in any order. Themicroemulsion blend is considered to be extremely fine colloidaldispersions consisting of micelles, or “bubbles,” of water and alcoholcoated with a layer of surfactant.

Thereafter, at step 108, the fuel composition is formed or formulated byadding to the fuel and the microemulsion blend having at least one oflower grade fatty acid derivatives being present in an amount effectivefor the fuel, alcohol, and water components to form the microemulsionblend. The blend may include a mixture of oleic acid, ethanol, ammonia,water, and cetane enhancer.

These steps may be performed under conditions that would tend not tosubstantially reduce an unsaturated fatty acid or fatty chloride. Suchconditions may include performing one or more of the steps in an inertatmosphere, such as a nitrogen atmosphere, or performing one or more ofthe steps in the absence of light.

FIG. 2A shows a method 200 for formulating a fuel composition on largescale. The method 200 may include refining crude oil 202 and through oneor more refining process fuel is derived. The fuel can be straight rundiesel 204. Similarly, lower grade fatty acid derivatives, such as,oleic acid, ethanol, and bi products of crude oil such as ammonia,water, along with cetane enhancer are blended to form microemulsionblend 206. The microemulsion blend 206 may include at least one of lowergrade fatty acid derivatives that may be present in an amount effectivefor the fuel 204, alcohol, and water components to form a microemulsionblend 206. The fatty acid can be oleic acid. Then, at least 57 to 99% offuel 204 i.e. diesel can be blended with 43-1% of microemulsion blend206 to formulate a fuel composition 208. The method 200 may also includeassessing the quality of the microemulsion blend 206 that can be done byanalyzing at least one of an oxidative stability and contaminates in themicroemulsion blend 206.

FIG. 2B depicts an apparatus 210 for formulating fuel composition. Theapparatus 210 may include a first container 214 and a second container216 for storing diesel/fuel 204 and microemulsion blend 206respectively. The straight run diesel 204 may be stored in the firstcontainer 214. The diesel 204 and the microemulsion blend 206 may be fedinto the first and second containers 214-216 respectively. The firstcontainer 214 and the second container 216 may be connected to one ormore blending containers 212A-N through one or more pipelines 218A-N.And the diesel 204 can be a straight run diesel or an unadditizeddiesel. The content of first and second containers 214-216 may besupplied through the connecting pipelines 218A-N to one or more blendingcontainers 212A-N. In the blending containers 212A-N, the microemulsionblend 206 may be blended with fuel, water, ammonia, cetane enhancer, andalcohol to form the fuel composition 208 (final product). Themicroemulsion blend 206 may be blended in different volumes with thefuel 204 (or diesel) which can be 5%, 6%, 12%, and so forth.

The microemulsion blend 206 can be blended with lower grade diesel orfuel 204 by using inline blending process at a petroleum terminal. Theinline blending process includes blending of the microemulsion blend 206at the petroleum terminal(s) within one or more pipelines.Alternatively, the microemulsion blend 206 can be blended with lowergrade diesel/fuel 204 by performing splash blending at the petroleumterminal. The splash blending may include blending the microemulsionblend 206 in a storage container (See 702 in FIG. 7) and then blendingwith the diesel 204 in distribution vehicle to splash blend in atransportation tank (not shown). The microemulsion blend may also beblended with the fuel by performing splash blending at a distributor byblending microemulsion blend 206 when blending the diesel (or fuel) 204to have the fuel composition 208 for distribution.

FIG. 2C illustrates another view of the apparatus 210 for formulatingfuel composition at large scale.

FIGS. 3A-3B illustrate a blending apparatus 300 for blending fuel andmicroemulsion blend for formulating fuel composition. The microemulsionblend comprises a mixture of oleic acid, ethanol, ammonia, water, andcetane enhancer. The fuel can be diesel which is at least one of astraight run diesel or an unadditized diesel. As shown in FIG. 3A, theblending apparatus 300 may include a first container 302 for storingfuel and a second container 304 for storing microemulsion blend. Thesecond container 304 may include an inlet/outlet pipeline 310.Similarly, the first container 302 may include an inlet/outlet pipeline312 as shown in FIG. 3B. The first and second containers 302-304 may beconnected to one or more blending containers 308A-N through a number ofpipelines 306A-N. The microemulsion blend volumes which are blended withthe lower grade diesel component can be such as, but not limited to, 5%,6%, and 12%. The microemulsion blend may be blended with the lower gradefuel by performing processes such as, but not limited to, inlineblending at a petroleum terminal, splash blending at the petroleumterminal, and splash blending at a distributor.

FIG. 4 shows a storage container 402 for storing the fuel compositionformed by blending the fuel, an alcohol, water, a cetane emulsifier, andmicroemulsion blend.

The invention is also described further in the Appendix to theSpecification.

In the preceding description, various aspects of claimed subject matterhave been described. For purposes of explanation, specific numbers,systems and/or configurations were set forth to provide a thoroughunderstanding of the claimed subject matter. However, it should beapparent to one skilled in the art having the benefit of this disclosurethat claimed subject matter may be practiced without the specificdetails. In other instances, features that would be understood by one ofordinary skill were omitted and/or simplified so as not to obscureclaimed subject matter. While certain features have been illustratedand/or described herein, many modifications, substitutions, changesand/or equivalents will now occur to those skilled in the art. It is,therefore, to be understood that the appended claims are intended tocover all such modifications and/or changes as fall within the truespirit of claimed subject matter.

We claim:
 1. A fuel composition for use in internal-combustion engines,the fuel composition comprising: a fuel component; an alcohol component;a water component a microemulsion blend comprising at least one of lowergrade fatty acid derivatives being present in an amount effective forthe fuel, alcohol, and water components to form a microemulsion blend;and a cetane-enhancer component.
 2. The fuel composition of claim 1,wherein the alcohol component is selected from a group of a lower gradeethanol or hydrous ethanol.
 3. The fuel composition of claim 2, whereinthe microemulsion blend is blended with lower grade diesel to form thefuel composition.
 4. The fuel composition of claim 3, wherein the fuelis diesel which is at least one of a straight run diesel or anunadditized diesel.
 5. The fuel composition of claim 4, wherein themicroemulsion blend volumes which are blended with the lower gradediesel component is at least one of 5%, 6%, and 12%.
 6. The fuelcomposition of claim 5, wherein the microemulsion blend comprisesrenewable components.
 7. The fuel composition of claim 6, wherein themicroemulsion blend comprises a mixture of oleic acid, ethanol, ammonia,water, and a cetane enhancer.
 8. A method of formulating a fuelcomposition for use in internal-combustion engines, the methodcomprising: providing a fuel; and forming the fuel composition by addingto the fuel, a microemulsion blend comprising at least one of lowergrade fatty acid derivatives being present in an amount effective forthe fuel, alcohol, and water components to form the microemulsion blend,wherein the microemulsion blend includes mixture of oleic acid, ethanol,ammonia, water and cetane enhancer.
 9. The method of claim 8 furthercomprising blending the microemulsion blend with lower grade diesel byperforming at least one of the following processes: inline blending at apetroleum terminal, the inline blending comprises blending of themicroemulsion blend at the petroleum terminals within one or morepipelines; splash blending at the petroleum terminal, the splashblending comprises blending the microemulsion blend in storage containerand then blending with the diesel component in distribution vehicle tosplash blend in a transportation tank; and splash blending at adistributor by blending microemulsion blend with the diesel component tohave the fuel composition for distribution.
 10. The method of claim 8further comprising assessing the quality of the microemulsion blend. 11.The method of claim 10, wherein the quality is assessed by analyzing atleast one of an oxidative stability and contaminates in themicroemulsion blend.
 12. The method of claim 11 further comprisingoptimizing the microemulsion blend volumes to be blended with differentquality of the diesel.
 13. The method of claim 12, wherein alcoholcomponent comprises at least one of an ethanol, or hydrous ethanol. 14.The method of claim 13, wherein the diesel is at least one of a straightrun diesel or an unadditized diesel.
 15. The method of claim 14, whereinthe microemulsion blend volumes which are blended with the lower gradediesel component is at least one of 5%, 6%, and 12%.
 16. The method ofclaim 15, wherein the microemulsion blend comprises renewablecomponents.